Ultra-fast aqueous polymerisation of acrylamides by high power visible light direct photoactivation RAFT polymerisation

The effect of visible LED power (λmax = 402 nm, 451 nm) on kinetics and control of direct photoactivation RAFT polymerisations of acrylamide and dimethylacrylamide are investigated. By increasing power supplied to the LEDs from 6 to 208 W, the polymerisation time required to reach >85% conversion is reduced from 12 hours to 11 minutes for acrylamide. Similar conversions are shown to be obtainable in 5 minutes for dimethylacrylamide, all without any exogenous photoinitiator or catalyst. This increase in polymerisation rate is attributed to an increase in both photon flux and a coincident increase in polymerisation temperature at higher light intensities. With both 402 nm and 451 nm LEDs exciting the same n → π* electronic transition, little difference in rate of polymerisation is seen between the two light sources. Minimal reduction in polymerisation control is observed at high irradiation intensity for acrylamide, while an increased production of low molecular weight dead chains is observed for dimethylacrylamide. This is shown to be mitigated by controlling the polymerisation temperature to 17 °C which caused both a reduction in low molecular weight tailing and an increased polymerisation time. Visible light direct photoactivation RAFT is also shown to have application in the synthesis of ultra-high molecular weight acrylamide polymers (Mn > 1 000 000 g mol−1)

Cleavage of macromolecular RAFT chain transfer agents by sodium azide during characterization by aqueous GPC

Accurate and reliable analysis of polymers by GPC is vital in the field of controlled radical polymerisation. Often, water-soluble polymers are analysed by aqueous gel permeation chromatography (GPC) in a solvent containing dilute sodium azide as an anti-microbial agent. Previous reports have shown that sodium azide at high concentration is able to remove terminal CTA groups from polymer chains, producing thiol-terminated polymers. This study demonstrates that GPC sample preparation of RAFT polymers in aqueous solvents containing dilute (200 ppm) sodium azide can cause significant changes in the measured molecular weight distribution. These changes occur within hours of dissolving the polymer sample and are shown to be due to cleavage of the CTA in the polymer chain together with disulfide coupling of the resulting polymeric thiols. The extent to which this occurs is strongly dependent on the CTA attached to the polymer; an almost 10-fold difference in the rate of CTA removal is observed between different RAFT agents. The by-product of the reaction between sodium azide and RAFT polymers is also investigated and shown to be an unstable thiatriazole-functionalised Z group. The thiatriazole then degrades further to form a nitrile-functionalised Z group, N2 and elemental sulfur

Achieving equity through 'gender autonomy': the challenges for VET policy and practice

This paper is based on research carried out in an EU Fifth Framework project on 'Gender and Qualification'. The research partners from five European countries investigated the impact of gender segregation in European labour markets on vocational education and training, with particular regard to competences and qualifications. The research explored the part played by gender in the vocational education and training experiences of (i) young adults entering specific occupations in child care, electrical engineering and food preparation/service (ii) adults changing occupations

Observations of Cepheids with the MOST satellite: Contrast between Pulsation Modes

The quantity and quality of satellite photometric data strings is revealing details in Cepheid variation at very low levels. Specifically, we observed a Cepheid pulsating in the fundamental mode and one pulsating in the first overtone with the Canadian MOST satellite. The 3.7-d period fundamental mode pulsator (RT Aur) has a light curve that repeats precisely, and can be modeled by a Fourier series very accurately. The overtone pulsator (SZ Tau, 3.1 d period) on the other hand shows light curve variation from cycle to cycle which we characterize by the variations in the Fourier parameters. We present arguments that we are seeing instability in the pulsation cycle of the overtone pulsator, and that this is also a characteristic of the O-C curves of overtone pulsators. On the other hand, deviations from cycle to cycle as a function of pulsation phase follow a similar pattern in both stars, increasing after minimum radius. In summary, pulsation in the overtone pulsator is less stable than that of the fundamental mode pulsator at both long and short timescales.Comment: accepted in MNRAS, 11 pages, 10 figure

Current Status of the SuperWASP Project

We present the current status of the SuperWASP project, a Wide Angle Search for Planets. SuperWASP consists of up to 8 individual cameras using ultra-wide field lenses backed by high-quality passively cooled CCDs. Each camera covers 7.8 x 7.8 sq degrees of sky, for nearly 500 sq degrees of sky coverage. SuperWASP I, located in LaPalma, is currently operational with 5 cameras and is conducting a photometric survey of a large numbers of stars in the magnitude range ~7 to 15. The collaboration has developed a custom-built reduction pipeline and aims to achieve better than 1 percent photometric precision. The pipeline will also produce well sampled light curves for all the stars in each field which will be used to detect: planetary transits, optical transients, and track Near-Earth Objects. Status of current observations, and expected rates of extrasolar planetary detections will be presented. The consortium members, institutions, and further details can be found on the web site at: http://www.superwasp.org.Comment: 3 pages, 2 figures, submitted to the Proceedings of the 13th Cool Stars Workshop, Ed. F. Favata, ESA-S

New periodic variable stars coincident with ROSAT sources discovered using SuperWASP

We present optical lightcurves of 428 periodic variable stars coincident with ROSAT X-ray sources, detected using the first run of the SuperWASP photometric survey. Only 68 of these were previously recognised as periodic variables. A further 30 of these objects are previously known pre-main sequence stars, for which we detect a modulation period for the first time. Amongst the newly identified periodic variables, many appear to be close eclipsing binaries, their X-ray emission is presumably the result of RS CVn type behaviour. Others are probably BY Dra stars, pre-main sequence stars and other rapid rotators displaying enhanced coronal activity. A number of previously catalogued pulsating variables (RR Lyr stars and Cepheids) coincident with X-ray sources are also seen, but we show hat these are likely to be misclassifications. We identify four objects which are probable low mass eclipsing binary stars, based on their very red colour and light curve morphology

Hobson’s choice? Constraints on accessing spaces of creative production

Successful creative production is often documented to occur in urban areas that are more likely to be diverse, a source of human capital and the site of dense interactions. These accounts chart how, historically, creative industries have clustered in areas where space was once cheap in the city centre fringe and inner city areas, often leading to the development of a creative milieu, and thereby stimulating further creative production. Historical accounts of the development of creative areas demonstrate the crucial role of accessible low-cost business premises. This article reports on the findings of a case study that investigated the location decisions of firms in selected creative industry sectors in Greater Manchester. The study found that, while creative activity remains highly concentrated in the city centre, creative space there is being squeezed and some creative production is decentralizing in order to access cheaper premises. The article argues that the location choices of creative industry firms are being constrained by the extensive city centre regeneration, with the most vulnerable firms, notably the smallest and youngest, facing a Hobson’s choice of being able to access low-cost premises only in the periphery. This disrupts the delicate balance needed to sustain production and begs the broader question as to how the creative economy fits into the existing urban fabric, alongside the competing demands placed on space within a transforming industrial conurbation

Infinite motion and 2-distinguishability of graphs and groups

A group A acting faithfully on a set X is 2-distinguishable if there is a 2-coloring of X that is not preserved by any nonidentity element of A, equivalently, if there is a proper subset of X with trivial setwise stabilizer. The motion of an element a in A is the number of points of X that are moved by a, and the motion of the group A is the minimal motion of its nonidentity elements. When A is finite, the Motion Lemma says that if the motion of A is large enough (specifically at least 2 log_2 |A|), then the action is 2-distinguishable. For many situations where X has a combinatorial or algebraic structure, the Motion Lemma implies that the action of Aut(X) on X is 2-distinguishable in all but finitely many instances. We prove an infinitary version of the Motion Lemma for countably infinite permutation groups, which states that infinite motion is large enough to guarantee 2-distinguishability. From this we deduce a number of results, including the fact that every locally finite, connected graph whose automorphism group is countably infinite is 2-distinguishable. One cannot extend the Motion Lemma to uncountable permutation groups, but nonetheless we prove that (under the permutation topology) every closed permutation group with infinite motion has a dense subgroup which is 2-distinguishable. We conjecture an extension of the Motion Lemma which we expect holds for a restricted class of uncountable permutation groups, and we conclude with a list of open questions. The consequences of our results are drawn for orbit equivalence of infinite permutation groups

Nutritional Ketosis Alters Fuel Preference and Thereby Endurance Performance in Athletes.

Ketosis, the metabolic response to energy crisis, is a mechanism to sustain life by altering oxidative fuel selection. Often overlooked for its metabolic potential, ketosis is poorly understood outside of starvation or diabetic crisis. Thus, we studied the biochemical advantages of ketosis in humans using a ketone ester-based form of nutrition without the unwanted milieu of endogenous ketone body production by caloric or carbohydrate restriction. In five separate studies of 39 high-performance athletes, we show how this unique metabolic state improves physical endurance by altering fuel competition for oxidative respiration. Ketosis decreased muscle glycolysis and plasma lactate concentrations, while providing an alternative substrate for oxidative phosphorylation. Ketosis increased intramuscular triacylglycerol oxidation during exercise, even in the presence of normal muscle glycogen, co-ingested carbohydrate and elevated insulin. These findings may hold clues to greater human potential and a better understanding of fuel metabolism in health and disease